Kinetic study of the isomerization reaction HCnN → HCn - 1NC (n = 1, 3 and 5)

Vichietti, R. M.; Haiduke, Roberto Luiz Andrade

doi:10.1093/mnras/stt2053

Cited by 5 publications

(4 citation statements)

References 36 publications

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“…The early experimental determinations of the energy separation between the isomers range from 10.3 22 to more than 17 kcal mol −1 , 23 but more recent work serves to reduce the uncertainty. Most theoretical predictions 15,20,32,34,35,38,42,46,52,62,67 support a value for ΔH f,298 °(HNC) − ΔH f,298 °(HCN) of 14.2−15.3 kcal mol −1 , in agreement with the experimental value of 14.8 kcal mol −1 from Pau and Hehre. 24 The Pau and Hehre results were questioned by Wenthold 45 based on revisions in the proton affinity scale in later years.…”

Section: Calculationssupporting

confidence: 76%

“…While the importance of HNC in combustion systems has attracted only modest interest, − ,, the properties of HNC have been studied extensively − in part as a result of its small size, which allows for study at high levels of theory, and in part as a result of its potential importance in astrochemistry. The objective of the present work is to re-evaluate the HNC chemistry, with particular emphasis on HNC + O 2 , which is studied by ab initio methods, and assess the implications for modeling HCN oxidation in combustion.…”

Section: Introductionmentioning

confidence: 99%

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Importance of the Hydrogen Isocyanide Isomer in Modeling Hydrogen Cyanide Oxidation in Combustion

Glarborg

Marshall

2017

Energy Fuels

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Hydrogen isocyanide (HNC) has been proposed as an important intermediate in oxidation of hydrogen cyanide (HCN) in combustion, but details of its chemistry are still in discussion. At higher temperatures, HCN and HNC equilibrate rapidly, and being more reactive than HCN, HNC offers a fast alternative route of oxidation for cyanides. However, in previous modeling, it has been required to omit the HNC subset partly or fully in the reaction mechanisms to obtain satisfactory predictions. In the present work, we re-examine the chemistry of HNC and its role in combustion nitrogen chemistry. The HNC + O 2 reaction is studied by ab initio methods and is shown to have a high barrier. Consequently, the omission of this reaction in recent modeling studies is justified. With the present knowledge of the HNC chemistry, including an accurate value of the heat of formation for HNC and improved rate constants for HNC + O 2 and HNC + OH, it is possible to reconcile the modeling issues and provide a satisfactory prediction of a wide range of experimental results on HCN oxidation. In the burned gases of fuel-rich flames, HCN and the CN radical are partially equilibrated and the sequence HCN ⎯ → ⎯⎯ +M HNC ⎯ → ⎯⎯⎯ +OH HNCO is the major consumption path for HCN. Under lean conditions, HNC is shown to be less important than indicated by the early work by Lin and co-workers, but it acts to accelerate HCN oxidation and promotes the formation of HNCO.

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Section: Calculationssupporting

confidence: 76%

Section: Introductionmentioning

confidence: 99%

Importance of the Hydrogen Isocyanide Isomer in Modeling Hydrogen Cyanide Oxidation in Combustion

Glarborg

Marshall

2017

Energy Fuels

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“…The equilibrium geometries of transition states for single‐step reactions already studied by Vichieti et al 60–62 and others investigated by Truhlar and collaborators 63 were initially considered here. Namely, the reactions selected are CO + H 2 ↔ H 2 CO, CO + H 2 O ↔ HCOOH, HCN ↔ HNC, H + F 2 ↔ HF + F, H + N 2 ↔ HN 2 , and H + CO↔HCO.…”

Section: Methodsmentioning

confidence: 99%

“…The equilibrium geometries of transition states for single-step reactions already studied by Vichieti et al [60][61][62] and others investigated by Truhlar and collaborators 63 were initially considered here.…”

Section: Methodsmentioning

confidence: 99%

The performance of exchange—correlation functionals in describing electron density parameters of saddle point structures along chemical reactions

Macedo

Haiduke

2022

J Comput Chem

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This work is focused on evaluating the performance of exchange-correlation functionals from density functional theory in providing descriptor values derived from the electron density of saddle point structures (transition states) in chemical reactions.The properties investigated were obtained from the quantum theory of atoms in molecules, including atomic charges and electron density topological data at the bond critical points. In addition, parameters from the Interacting quantum atom energy partition were used as well in this comparative study. The reference values are attained in coupled cluster calculations with iterative single and double excitations (CCSD).

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Providing theoretical data for detection of four formamidic acid isomers in astrophysical media

Vichietti

Silva

Haiduke

2018

Molecular Astrophysics

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Kinetic study of the isomerization reaction HCnN → HCn - 1NC (n = 1, 3 and 5)

Cited by 5 publications

References 36 publications

Importance of the Hydrogen Isocyanide Isomer in Modeling Hydrogen Cyanide Oxidation in Combustion

Importance of the Hydrogen Isocyanide Isomer in Modeling Hydrogen Cyanide Oxidation in Combustion

The performance of exchange—correlation functionals in describing electron density parameters of saddle point structures along chemical reactions

Providing theoretical data for detection of four formamidic acid isomers in astrophysical media

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